Development,growth, and adhesion of Al2O3 on platinum-aluminum alloys

The development, growth, and adhesion of -Al₂O₃ scales on platinum-aluminum alloys containing between 0.5 and 6 wt.% aluminum have been studied at temperatures in the interval between 1000 and 1450° C. The morphologies and microstructures of the -Al₂O₃ scales were found to be influenced by the temperature, oxygen pressure, and the microstructures of the alloys. The oxidation rates of the alloys appeared to be controlled by transport of oxygen along grain boundaries in the -Al₂O₃ scales. The -Al₂O₃ scales adhered to the platinum-aluminum substrates even after extensive periods of cyclic oxidation. The good adhesion of the -Al₂O₃ may result from mechanical keying of the oxide to the alloys due to the development of irregular oxide-alloy interfaces.This work was supported by the U.S. Army Research Office, Durham, under Contract Number DAHCO 4 73 C 0021.     

The effect of Mo on the high-temperature sulfidation of Ni

The sulfidation behavior of Ni-Mo alloys containing up to 40 wt.% Mo was studied at =0.01 atm. over the temperature range of 550–800°C. The alloys included two solid solutions (Ni-10Mo and Ni-20Mo), the single-phase intermetallic compound Ni₄Mo(Ni-29Mo), and two alloys which were two-phase, Ni-30Mo and Ni-40Mo (Ni₄Mo+Ni₃Mo). The sulfidation of all alloys followed the parabolic rate law. The rate of sulfidation decreased with increasing amounts of Mo. Activation energies for sulfidation gave values of 39.1±1.0 kcal/mol. The sulfide scales were bilayered, consisting of an outer layer nickel sulfide (NiS_1+x and Ni₃S₂) and an inner, complex layer of MoS₂ plus intermetallic particles. The rate-controlling step of the sulfidation for the alloys was inward sulfur diffusion and/or outward nickel diffusion through the inner MoS₂ layer. Neither selective sulfidation nor internal sulfidation were observed. No significant difference in the sulfidation kinetics, sulfide structure, and scale constitution could be noted between single-phase alloys and two-phase alloys. The location of the markers was the interface between the inner and outer layers, indicating that the inner layer formed by inward diffusion of sulfur, and the outer layer grew by outward nickel diffusion. The inability to form a continuous protective molybdenum sulfide layer is discussed in terms of the structure of MoS₂ and changes caused by intercalation of Ni into the layered crystal structure. The decrease in sulfidation rate with increasing Mo was attributed to increasing amounts of the intermetallic compound. The increasing volume fraction of particles decreased the available diffusion area in the inner layer and provided a blocking effect.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

The hot corrosion of directionally solidified Ni-Cr-Nb-Al (γ/γ′-δ) eutectic alloys

The hot-corrosion resistance of two /- eutectic alloys, Ni-23.1 Nb-4.4 Al and Ni-19.7Nb-6Cr-2.5 Al, has been studied using three techniques: (1) a salt-coated test, in which the specimens are coated with a thin layer of Na₂SO₄ and oxidized; (2) the Dean rig test, in which salt is evaporated into the gas stream and allowed to condense continuously on the specimen; and (3) a sulfidation/oxidation test, in which the specimens were presulfidized for a short time in a H₂/H₂S mixture and then oxidized. The salt-coated test suggested that these alloys are generally quite resistant to sodium-sulfateinduced corrosion, although localized severe attack was sometimes encountered. The morphology of the corrosion products suggested that the mechanism of the attack was sulfidation/oxidation, and that salt fluxing mechanisms were relatively unimportant. In the Dean rig test it was shown that sodium chloride greatly increased the severity of attack, as has been shown earlier for alumina-forming superalloys.     

Oxidation ofγ′-Ni3Al andγ′-Ni3Al(Si) intermetallic compounds at low-oxygen pressures

The oxidation behavior of -Ni₃Al and -Ni₃Al(Si) (Ni₇₅Al₂₀Si₅) intermetallic compounds was studied at 1073 K and oxygen partial pressures of 59×10^–6 atm, 1.2×10^–14 atm, and 1.2×10^–19 atm by means of a manometric apparatus, and Rhines packs of NiO/Ni and FeO/Fe, respectively. Oxidation kinetics were determined either by recording weight gains or by measuring the internal-oxidation-zone depths. The structures and morphologies of oxides were also studied. Relatively low oxidation rates occurred for both compounds when oxidized in the manometric apparatus, while fast internal oxidation was observed for both compounds in the NiO/Ni pack. The fastest oxidation occurred in the -Ni₃Al compound in the FeO/Fe pack. A healing Al₂O₃ layer was formed on the surface of -Ni₃Al(Si) compound in the FeO/Fe pack, indicating a synergistic effect between the solute elements in the compound at the oxygen pressures corresponding to the dissociation of FeO. The oxidation rate was found to depend on the volume expansion associated with solute-atom oxidation.     

The corrosion behavior of Co-Mo alloys in H2-H2O-H2S environments

The corrosion behavior of Co alloyed with up to 40 wt.% Mo alloys was studied in H₂-H₂O-H₂S gas mixtures over the temperature range between 600C and 900C. The parabolic rate constants for corrosion decreased with increasing amounts of Mo. The compositions of all gas atmospheres fall in the sulfide(s stability region of the ternary M-O-S phase diagrams at all temperatures investigated. All the corrosion scales were composed of sulfides, while no oxide was detected. The sulfide scales formed were duplex at all temperatures except at 900C. The outer layer consisted primarily of cobalt sulfide, while the inner layer was complex and heterophasic, the phases formed being highly composition dependent. MoS₂ predominated in the inner layer for all alloys. However, a metallic Mo layer was formed in the innermost layer of Co-40 Mo. Activation energies were different for all alloys, increasing with increasing Mo content. Identical kinetics were observed for Co-30Mo corroded at 700–800C. A Chevrel-phase Co_1.62Mo₆S₈ was present in scales formed on the samples exhibiting the temperature-independent kinetics. A possible model in which Co_1.62Mo₆S₈ forms preferentially in H₂-containing mixed gas is suggested. Alloys corroded at 900C formed a lamellar-structure scale which contained Co and CoMo₂S₄ layers perpendicular to the alloy surface. A eutectoid decomposition of an unknown Co-Mo sulfide may be responsible for the presence of the lamellar structure.     

The formation of α-Al2O3 scales at 1500°C

The growth of Al₂O₃ scales on -NiAl was studied at 1500°C. Oxidation rates, diffusion mechanisms, and microstructures were examined in order to achieve a complete understanding of the scale development. Variation of the Al content within the phase field had little effect on the oxidation behavior. Ionimplanted yttrium (2×10¹⁶/cm²) was observed to provide a short-term improvement in scale adhesion but little long-term effect. When doped with Y or Zr, the first 1 m of -Al₂O₃ was observed to grow mainly by an inward oxygen growth mechanism. At longer times when the implant was ineffective, microstructural observations indicate a mixed-growth mode.     

TEM Study of Scale Microstructures Formed on Ni–10Cr and Ni–10Cr–5Al Alloys with and Without Y Addition

A study was conducted to investigate the effect of Y addition on the isothermal-oxidation behaviors of Ni–10Cr, Ni–10Cr–0.5Y, Ni–10Cr–5Al, and Ni–10Cr–5Al–0.5Y alloys. The alloys were oxidized in air for 50 hr at 1000°C. The oxides formed on the alloys were characterized using primarily cross-sectional transmission-electron microscopy techniques along with light microscopy, scanning-electron microscopy, and X-ray diffraction. Although the Al-containing alloys showed comparatively better oxidation behavior, all alloys exhibited nonprotective scaling, as suggested by the thick oxides formed. The major component of the outer oxide was NiO. However, modified Y-containing alloys formed protective layers (i.e., -Cr₂O₃ for NiCrY and -Al₂O₃ for NiCrAlY) at the scale–alloy interface following the nonprotective scaling. The spalling resistance of the modified Y-containing alloys was better than their counterpart unmodified Y-free alloys, while their overall oxidation mechanism remained unchanged after Y addition.     

Age hardening of VT35 titanium alloy

VT35 alloy belongs to -titanium alloys that preserve the body-centered lattice of the -phase in hardening from the -region. In an equilibrium state this alloy has an + structure. After hardening, VT35 alloy has a high ductility and a low strength. The subsequent single- or double-stage aging in the biphase region promotes considerable strengthening of the alloy due to segregation of a second phase. VT35 titanium alloy is hardened to a pure -phase by cooling from the single-phase region in water, in air, or with the furnace (at a rate of at least 3 -4 deg/min). This special feature of the alloy is caused by its chemical composition (Ti - 3% Al -15% V - 3% Cr - 3% Sn), which provides a high coefficient of -stabilizationK = 1.5. The present paper concerns the processes of age toughening of a hardened VT35 alloy and the kinetics of the structural transformations in such a treatment.     

Formation of elemental silicon inclusions in the sulfide scale on Cu-Si alloys

The sulfidation of Cu-Si alloys in liquid sulfur resulted in an enrichment in the metallic substrate in silicon with the simultaneous formation of the phase, whereas within the inner layer of the scale elementary silicon occurred in a dispersed form. The formation of the phase in the surface layer of the metallic substrate results from the supersaturation of vacancies generated at the alloy/scale interface. The formation of silicon inclusions results in the selective sulfidation of copper when the phase moves toward the inner layer of the scale.Formerly of Institute of Materials Engineering, Academy of Mining and Metallurgy, Cracow, Poland.     

Kinetics and mechanisms of the oxidation of cobalt at 600–800°C

Two-phase layered scales comprising CoO and Co ₃O₄ formed on cobalt during oxidation at 600°, 700°, and 800°C and at oxygen partial pressures in the range 0.001–1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, non-parabolic stage of oxidation. The monoxide consisted of relatively large grains (10 ) and the spinel comprised small grains (3 ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinel layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co₃O₄.     

On the nature of “easy paths” for the diffusion of oxygen in thermal oxide films on aluminum

Thermal oxide films grown on electropolished aluminum specimens have been investigated by transmission electron microscopy of stripped oxide films and ultramicrotomed sections. Particular attention has been focused on the nucleation sites -Al ₂ O ₃ crystals and the relationship of such sites to surface features on the electropolished aluminum surface. It is evident that easy paths for the diffusion of oxygen, or the nucleation sites of -Al ₂ O ₃ crystals, are not distributed randomly over the electropolished aluminum surface, but form preferentially in the amorphous oxide layer grown over preexisting metal ridges. Thus, the diffusion of molecular oxygen through cracks in the amorphous oxide layer represents the most realistic and acceptable basis for explaining the local growth of the -Al ₂ O ₃ crystals in thermal oxide films on aluminum, although the cracks have not yet been observed directly.Present address: Alcan International, Ltd., Banbury Laboratories, Banbury, Oxford, OX16 7SP, United Kingdom.     

High-temperature oxidation behavior of pure Ni3Al

The high-temperature oxidation behaviour of pure Ni₃Al alloys in air was studied above 1000°C. In isothermal oxidation tests between 1000 and 1200°C, Ni₃Al showed parabolic oxidation behavior and displayed excellent oxidation resistance. In cyclic oxidation tests between 1000 and 1300°C, Ni₃Al exhibited excellent oxidation resistance between 1000 and 1200°C, but drastic spalling of oxide scales was observed at 1300°C. When Ni₃Al was oxidized at 1000°C, Al₂O₃ was present as -Al₂O₃ in a whisker form. But, at 1100°C the gradual transformation of initially formed metastable -Al₂O₃ to stable -Al₂O₃ was observed after oxidation for about 20 hr. After oxidation at 1200°C for long times, the formation of a thick columnar-grain layer of -Al₂O₃ was observed beneath a thin and fine-grain outer layer of -Al₃O₃. The oxidation mechanism of pure Ni₃Al is described.     

Analytical study of surface and bulk oxidation of Astroloy

Nickel-base alloys, such as Astroloy, used for aeronautical turbine disks, are sensitive to time-dependent cracking in environments containing oxygen. The mosaic structure of the alloy consisting islands (200 nm average size) surrounded by the -phase (100 nm thick) induces complex oxidation phenomena. Various analytical approaches allow the delineation of all the steps from segregation to oxidation occurring on the surface of such a duplex structure. The protection of Astroloy by its outer oxide layer against oxygen penetration was studied also, using alternative ¹⁶O₂ then ¹⁸O₂ oxidation. In association with STEM studies, it is shown that the outer oxide scale is not a real barrier against oxygen penetration and that inner precipitation of chronium (+ aluminium and titanium)-enriched oxides, takes place especially in the structure.     

18O/SIMS characterization of the growth mechanism of doped and undoped α-Al2O3

Sequential oxidation experiments at 1200°C and 1500°C using¹⁶O and >95%¹⁸O-enriched environments were conducted on undoped and Y- and Zr-doped -NiAl and FeCrAl alloys. After oxidation, samples were analyzed by SIMS sputter depth profiling. At 1200°C, a clear pattern was established where the undoped -Al₂O₃ was found to grow by the simultaneous transport of both Al and O. Zr-doped -Al₂O₃ was found to grow mainly by the inward transport of oxygen. The profiles in all cases indicate O diffusion primarily by shortcircuit pathways. Results at 1500°C (only on -NiAl) indicated a similar behavior but were less conclusive. Y and Zr were found to segregate to the oxide grain boundaries at 1200°C and 1500°C. The segregation of these dopants is believed to impede the cation transport in the -Al₂O₃ scale and thereby change the oxidation mechanism.     

The effect of various oxide dispersions on the phase composition and morphology of Al2O3 scales grown on β-NiAl

A series of oxide-dispersed-NiAl alloys were oxidized in order to explore the effect of various cation dopants on the - phase transformation in the Al₂O₃ scale and the effect of phase composition on the scale microstructure. Larger ions such as Y, Zr, La, and Hf appeared to slow the- to-Al₂O₃ phase transformation, while a smaller ion, Ti, appeared to accelerate the transformation.     

General laws governing variation in properties of cast alloys of the Al-Zn-Mg system

Among existing high-strength corrosion-resistant aluminum alloys, those of the Al-Mn-Zn system are most promising. They have a different phase composition, depending on the content of magnesium and Zinc: + (Al₃Mg₂), + + T(Al₂Mg₃Zn₃), + T, + T + (MgZn2) and + The majority of industrial Al-Mg-Zn alloys correspond to the phase regions + T and + T + with respect to composition. A high level of strength and satisfactory overall corrosion resistance are characteristic for these alloys. Al-Mg-Zn alloys may, however, tend to the most dangerous form of corrosion - stress-induced corrosion cracking. Using methods of experiment planning in the study, we investigated Al-Zn-Mg alloys of various compositions for the purpose of selecting alloy compositions with a high level of mechanical properties and stress-induced corrosion cracking.All-Union Scientific-Research Institute of Aviation Materials. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 12, pp. 24–28, December, 1994.     

The air oxidation of an austenitic Fe-Mn-Cr stainless steel for fusion-reactor applications

The oxidation in air of an austenitic Fe-Mn-Cr steel containing 17.8 Mn, 9.5 Cr, 1.0 Ni, 0.27 C, and 0.03 N was studied over the range 700–1000°C. Oxidation of surface-abraded samples at low temperatures, 700–750°C, resulted in only Mn ₂O₃ containing dissolved chromium, except at corners, where large nodules containing spinel and manganowustite formed. The Mn₂O₃ layer grew into the substrate forming a globular-type film. This growth mode was the result of slow interdiffusion in the alloy after the cold-worked surface layer had been recrystallized and/or consumed, as evidenced by the formation of a ferrite layer subjacent to the scale and by the instability of the planar interface. No internal oxidation was observed beneath the Mn₂O₃ film at either 700 or 750°C. Samples oxidized in thehigh-temperature region, 800–1000°C, exhibited vastly different behavior, forming thick stratified scales at long times (24 hr), the scales consisting of a very thin outer layer of Mn₂O₃ (with appreciable iron in solution), Fe-Mn spinel beneath the outer layer, and a thick inner layer of manganowustite and a chromium-containing spinel. No chromium was found in the outer two layers. A thin layer of nearly pure Fe₂O₃ formed between Mn₂O₃ and the outer spinel. Quasiparabolic kinetics were observed. The high-temperature rates were about 10³ to 10⁴ times greater than at low temperatures at the transition temperature. The rapid rates at high temperatures were attributed to manganowustite growth. However, oxidation of an electropolished sample at 750°C, from which the superficial cold-worked layer had been removed, formed scales similar to those observed at high temperatures at comparable rates. A difference by a factor of over 10⁴ existed between the oxidation rate of the electropolished sample and the surface-abraded sample at 750°C. The much slower oxidation rate of the latter is attributed to greatly enchanced manganese diffusion through the high dislocation-density, cold-worked layer. Short-time tests at 800°C revealed an incubation period during which a thin protective layer of Mn²O₃ formed. The incubation period corresponded to the recrystallization time of the cold-worked layer. Subsequently, nodular growth occurred which was associated with internal oxidation. The nodules, consisting of spinel and manganowustite, eventually linked up to form a thick, stratified scale. Comparison of the scale structures with calculated phase diagrams of composition versus oxygen activity (at constant temperature), showed that the protective films formed at low temperatures were due to kinetics factors, involving enhanced manganese diffusion through the cold-worked layer, rather than to thermodynamics. A model for the breakdown of protective films is proposed which involves internal oxidation.     

Oxidation and intergranular disintegration of the aluminides NiAl and NbAl3 and phases in the system Nb-Ni-Al

The oxidation behavior is very different for an aluminide with a wide homogeneity range such as -NiAl than for a line compound such as NbAl ₃.Oxidation of -NiAl at temperatures 1273 K leads to a slow-growing -alumina layer. The metal phase beneath the scale remains as -NiAl; however, cavity formation is observed. The cavity formation may be favored by sulphur surface segregation. Oxidation of NbAl ₃ at temperatures 1273 K initially leads to -Al ₂O₃,but the Al depletion causes the formation of Nb ₂ Al beneath the oxide layer. Cracking of the Al ₂O₃ layer opens Nb ₂ Al to the atmosphere, which oxidizes rapidly to Nb ₂O₅ and NbAlO₄.After consumption of the Nb ₂ Al, a layer of Al ₂O₃ formed again on the NbAl ₃ phase, but failure of the alumina and the fast growth of the other oxides occur as a repeated process. Thus, NbAl ₃ exhibited rapid linear oxidation kinetics. Multiphase alloys in the system Nb-Ni-Al generally behave better than NbAl ₃,and the low oxidation rates of -NiAl can be approached. In the temperature range below 1273 K, with a maximum at 1000 K, both NiAl and NbAl ₃ show the pest phenomenon, an intergranular disintegration. Preceding the disintegration, oxygen diffuses into the grain boundaries of the material and Al ₂O₃ is formed at the grain boundaries, beginning from the surface region. NiAl is susceptible only in a very limited range of oxygen pressures and temperatures, whereas NbAl ₃ is much more susceptible.     

The corrosion behavior of Fe-Nb-Al alloys in H2/H2O/H2S atmospheres

The corrosion behavior of eight Fe-Nb-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S atmospheres. The corrosion kinetics followed the parabolic rate law for all alloys at all temperatures. The corrosion rates were reduced with increasing Nb content for Fe-x Nb -3Al alloys, the most pronounced reduction occurred as the Nb content increased from 30 to 40 wt.%. The corrosion rate of Fe-30Nb decreased by six orders of magnitude at 700°C and by five orders of magnitude at 800°C or above by the addition of 10 wt.% aluminum. The scales formed on low-Al alloys (3 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with Al dissolved near the outer-/inner-layer interface) and an inner complex layer of Fe_xNb₂S₄(FeNb₂S₄ or FeNb₃S₆), FeS, Nb₃S₄ (only detected for Nb contents of 30 wt.% or higher) and uncorroded Fe₂Nb. No oxides were detected on the low-Al alloys after corrosion at any temperature. Platinum markers were found to be located at the interface between the inner and outer scales for the low-Al alloys, suggesting that the outer scale grew by the outward transport of cations (Fe and Al) and the inner scale grew by the inward transport of sulfur. The scales formed on high-Al alloys (5 wt.% Al) were complex, consisting primarily of Nb₃S₄, Al₂O₃ and (Fe, Al)_xNb₂S₄, and minor amounts of (Fe, Al)S and uncorroded intermetallics (FeAl and Fe₂Nb). The formation of Nb₃S₄ and Al₂O₃ blocked the transport of iron through the inner scale, resulting in the significant reduction of the corrosion rates.